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• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/396—Distribution of the active metal ingredient
  • B01J35/399—Distribution of the active metal ingredient homogeneously throughout the support particle
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0063—Granulating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/031—Precipitation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/082—Decomposition and pyrolysis
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/16—Reducing
  • B01J37/18—Reducing with gases containing free hydrogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
  • C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

• the invention belongs to the technical field of catalytic hydrogenation, specifically relates to a catalyst for liquid phase hydrogenation of acetophenone to produce ⁇ -phenylethanol, and relates to the preparation method and use of the catalyst.
• ⁇ -Phenylethanol is an important chemical intermediate, which is widely used in industries such as medicine, perfume manufacturing, cosmetics, food and fine chemical.
• the existing methods for synthesizing ⁇ -phenylethanol mainly include microbial fermentation method and acetophenone reduction/catalytic hydrogenation method.
• the microbial fermentation method generally uses phenylalanine and fluorophenylalanine as raw materials, and produces ⁇ -phenylethanol through microbial fermentation transformation.
• the raw materials used in the microbial method are expensive and the production cost is high.
• acetophenone hydrogenation method is generally used in the production of ⁇ -phenylethanol in industry. This method has the advantages of low production cost, less by-products, high product yield and high product purity, and the method is suitable for large-scale production of ⁇ -phenylethanol.
• the acetophenone hydrogenation catalysts mainly include noble metal (such as platinum and palladium) catalysts, nickel-based catalysts, and copper-based catalysts.
• Noble metal catalysts and nickel-based catalysts have high costs, are liable to cause aromatic ring saturation and phenylethanol hydrogenolysis, and have poor selectivity to ⁇ -phenylethanol.
• copper-based catalysts when using for acetophenone hydrogenation reaction, have the advantages of high activity, high selectivity and low cost.
• US4996374 discloses a Pd-C catalyst, but the stability of the catalyst is poor, and it is necessary to continuously increase the reaction temperature when recycled.
• CN1315226A discloses a reduction treated copper-based catalyst and a method for preparing ⁇ -phenylethanol using the catalyst, but the catalyst requires a liquid phase reduction method to improve the stability thereof, which is complicated in process and costly.
• CN1911883A discloses a method for preparing ⁇ -phenylethanol using Raney nickel as a catalyst, but there is a large amount of aromatic ring hydrogenation product ⁇ -cyclohexylethanol in the acetophenone hydrogenation product, the selectivity to ⁇ -phenylethanol is low.
• EP0714877B1 uses carbonates of alkali metal and/or alkaline-earth metal to modify the copper-silicon catalyst, which significantly inhibits the formation of by-product ethylbenzene.
• the silicon source is added in the form of fumed silica or diatomaceous earth, which is detrimental to the enhancement of the interaction between the active component and the carrier, therefore detrimental to the strength of the catalyst.
• Some silicon sources in the catalyst of WO2016198379 are added in the form of silica sol during extrusion molding, which cannot effectively disperse the active component copper. None of the above-mentioned publications mentions the dispersing and stabilizing effects of the additives on the active components, the mechanical stability during use and strength after use of the molded catalysts.
• the acetophenone hydrogenation process is extremely prone to the side reactions of ⁇ -phenylethanol hydrogenolysis/dehydration to form ethylbenzene/styrene, the reaction rates of hydrogenolysis and dehydration increase rapidly with the increase of the reaction temperature.
• the liquid phase hydrogenation reaction at a lower temperature is usually selected. Therefore, the acetophenone hydrogenation catalyst is required to have good liquid resistance, weak acidity and good activity at low temperature.
• the copper-based catalysts for liquid phase hydrogenation reaction are not only subjected to various internal or external forces during storage/charging/reduction/reaction processes, but also subjected to significant decrease in strength during actual use due to liquid soaking, swelling and so on, which cause the catalyst to be easily crushed and powdered in the liquid phase hydrogenation system, threatening the stable operation of industrial units and affecting the life of the catalyst.
• the copper-based catalysts for acetophenone hydrogenation to produce ⁇ -phenylethanol prepared by the precipitation method usually have problems such as low dispersity of active component copper, strong acidity and weak interaction between the carrier and the active component, leading to low conversion rate of acetophenone, large amount of by-products such as ethylbenzene, poor selectivity to phenylethanol and poor catalyst strength. Therefore, improving the dispersity of the active component copper and the mass transfer performance of the catalyst, suppressing the acidity of the catalyst, and improving the liquid resistance of the catalyst are of great significance for the preparation of acetophenone hydrogenation catalyst with high activity, high selectivity and high liquid resistance.
• the purposes of the present invention is to provide a preparation method of a catalyst for producing ⁇ -phenylethanol by liquid phase hydrogenation of acetophenone, and a prepared catalyst.
• the catalyst prepared by the method significantly suppresses side reactions such as hydrogenolysis, and has high catalyst activity and high selectivity; at the same time, the catalyst has excellent liquid resistance and has high strength after reduction and liquid phase hydrogenation reaction.
• a preparation method for a hydrogenation catalyst comprising the following steps:
• step (1) aims at mixing deionized water, a small molecule alcohol, a Gemini surfactant, an organic pore-forming agent and a silica sol well to prepare an aqueous dispersion of silica sol containing the small molecule alcohol, the Gemini surfactant and the organic pore-forming agent, wherein, the organic pore-forming agent is preferably selected from one or more of PMMA, microcrystalline cellulose and methyl cellulose; the organic pore-forming agent is added during the preparation process to reduce the diffusion resistance in the raw materials and the product, and therefore effectively improve the activity and selectivity of the catalyst.
• the organic pore-forming agent is preferably selected from one or more of PMMA, microcrystalline cellulose and methyl cellulose
• the particle size of the organic pore-forming agent is ⁇ 100 ⁇ mm, more preferably 1-80 ⁇ m, and still more preferably 3-30 ⁇ m, such as 5, 10, 15, 20, or 25 ⁇ m. Keeping the particle size of the organic pore-forming agent within a suitable range will be conducive to further improving the diffusion mass transfer effect of the raw materials and the product. If the particle size is too large, it is not conducive to playing an effective role in improving the mass transfer performance; if the particle size is too small, it is not conducive to improving the mass transfer performance too.
• the amount of the organic pore-forming agent accounts for 0.5-20wt%, more preferably 1-10wt% and still more preferably 2-5wt% of the total weight of the catalyst. Keeping the amount of organic pore-forming agent in a suitable range will be conducive to minimizing the impact on the strength of the catalyst on the premise of achieving good mass transfer performance. If the amount of organic pore-forming agent is too small, it is not conducive to playing an effective role in improving the mass transfer performance; if the amount of organic pore-forming agent is too much, the mechanical strength of the catalyst will be affected.
• the total amount of silicon in the catalyst is introduced by the silica sol and the silicon containing alkaline precipitant together.
• the amount of silicon introduced by the silica sol accounts for 30-70wt%, more preferably 35-65wt%, still more preferably 40-60wt%, such as 50wt% of the total amount of silicon in the catalyst.
• the prepared catalyst is not only highly active but also has high strength.
• the silica sol is an alkaline silica sol, and the pH value is 8.0-10.0.
• the small molecular alcohol refers to an alcohol having a molecular weight of not more than 400, such as a small molecular saturated monohydric alcohol having a molecular weight of not more than 400.
• the mass ratio of the small molecule alcohol to deionized water is 1:20 to 1:10, such as 1:18, 1:15, or 1:12; further preferably, the small molecule alcohol in step (1) is one or more of methanol, ethanol, propanol and butanol.
• the used Gemini surfactant is well known in the art, and it is a new surfactant that connects two or more traditional surfactant molecules at a hydrophilic group or near a hydrophilic group through a linking group.
• the Gemini surfactant has at least two hydrophobic hydrocarbon chains, two polar head groups and a linking group; the linking group can be long, short, rigid, flexible, polar or non-polar; the Gemini surfactant can be divided into anionic-type, cationic-type, nonionic-type and zwitterionic-type Gemini surfactants depending on whether the polar head group is cationic, anionic or nonionic; the Gemini surfactant can be divided into symmetric Gemini surfactant and asymmetric Gemini surfactant based on the bipolar head group and hydrophobic chain structure.
• the Gemini surfactant in the step (1) is added in an amount of 0.1%-1% of the total mass of the deionized water and the small molecule organic alcohol.
• the specific type of Gemini surfactant used in the present invention is not particularly limited.
• the Gemini surfactant is a bromide having a structure of C m-n-m , wherein m is preferably 12, 14 or 16, and n is preferably 2, 3, 6, 8 or 10.
• the used Gemini surfactants can be obtained from the corresponding reagents available on the market, for example, which can be Gemini surfactants having a structure of C 16-6-16 , C 12-10-12 , C 14-8-14 , C 12-8-12 or C 14-10-14 , or Gemini surfactants having a structure of C 16-2-16 , C 12-3-12 , C 14-2-14 or C 12-3-12 , etc., purchased from Henan Daochun Chemical Co., Ltd.
• the dispersity of the silica sol is improved, such that the active component copper has higher dispersity, and the catalyst activity is improved.
• the Gemini surfactant can further cooperate with the organic pore-forming agent to promote the formation of mesoporous structure and improve the mass transfer performance of the catalyst.
• the precipitant refers to substance that can react with the metal cation in the solution of mixed salt to form corresponding precipitate.
• step (2) is to prepare a solution of mixed salt and an aqueous solution of alkaline precipitant, and add the two together to the aqueous dispersion of silica sol, so that the mixed salt become corresponding precipitate in the aqueous dispersion of silica sol containing the organic pore-forming agent.
• Studies have found that by dispersing the pore-forming agent in the silica sol in advance, and then forming a precipitate in the silica sol, it is beneficial to the better dispersion of the pore-forming agent in the precipitate.
• the silicon containing alkaline precipitant is a water soluble silicate, preferably one or two of sodium silicate and potassium silicate;
• the silicon free alkaline precipitant is one or more of potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydroxide, potassium hydroxide, ammonium carbonate, ammonium bicarbonate, carbamide and ammonia water.
• each metal salt forming the solution of mixed salt is a soluble salt of the corresponding metal.
• the salt of the copper containing compound is one or more of copper nitrate, copper chloride and copper acetate
• the salt of the zinc containing compound is one or more of zinc nitrate, zinc chloride and zinc acetate
• the salt of the rare-earth metal compound is one or more of nitrate, chloride and acetate
• the salt of the alkaline-earth metal compound is one or more of nitrate, chloride and acetate.
• Zn and Cu can form a "solid solution" during the preparation process, which can effectively promote the dispersion of the active component copper in the catalyst;
• the addition of a rare-earth metal also plays a role in improving the dispersity of the copper in the catalyst and the stability of the catalyst, preferably, the rare-earth metal is lanthanum and/or cerium;
• the addition of an alkaline-earth metal significantly inhibits the acidity of the catalyst, can effectively inhibit the formation of ethylbenzene, and improves the reaction selectivity, preferably, the alkaline-earth metal is one or two or more of magnesium, calcium and barium.
• each metal component is added in an amount such that the oxide in the prepared catalyst corresponding to each metal component reaches its target amount.
• the prepared catalyst contains 20-65 wt% of copper oxide, 15-50 wt% of silicon oxide, 2-25 wt% of zinc oxide, 0.1-5 wt% of rare-earth metal oxide and 0.5-15 wt% of alkaline-earth metal oxide; more preferably, the prepared catalyst contains 40-63 wt% of copper oxide, 20-45 wt% of silicon oxide, 5-20 wt% of zinc oxide, 0.2-3 wt% of rare-earth metal oxide and 0.5-10wt% of alkaline-earth metal oxide; still more preferably, the prepared catalyst contains 42-60 wt% of copper oxide, 22-40 wt% of silicon oxide, 10-18 wt% of zinc oxide, 0.5-2 wt% of rare-earth metal oxide and 1-5 wt% of alkaline-e
• step (2) the pH of the reaction system during the reaction process is controlled to 5.0-9.0, such as 5.5-8.0, and then the system is aged to obtain a slurry; preferably, the temperature of the reaction process and the aging process is controlled to 60-90 °C, such as 70 or 80 °C.
• the specific process for forming a precipitate through a reaction and the precipitate aging process are well known in the art, for example, the reaction process for forming a precipitate can be completed within 1-3 hours, and then aging for another 1-3 hours.
• step (3) the purpose of step (3) is to filter and wash the slurry to obtain a filter cake; the filtering and washing processes can all adopt the filtering and washing processes commonly used in the art, which are all processes commonly used for treating catalysts in the art.
• step (4) the drying, calcining, and molding processes for the filter cake are also commonly used processes for treating catalysts in the art; in one embodiment, the calcining temperature is 300-700 °C, such as 400, 500, or 600 °C; the calcining time is 4-12h, such as 6, 8 or 10h; the molding may be tablet molding and the like.
• the present invention also provides a catalyst prepared according to the above preparation method.
• the catalyst includes 20-65 wt% of copper oxide, 15-50 wt% of silicon oxide, 2-25 wt% of zinc oxide, 0.1-5 wt% of rare-earth metal oxide and 0.5-15 wt% of alkaline-earth metal oxide; more preferably, the catalyst includes 40-63 wt% of copper oxide, 20-45 wt% of silicon oxide, 5-20 wt% of zinc oxide, 0.2-3 wt% of rare-earth metal oxide and 0.5-10wt% of alkaline-earth metal oxide; still more preferably, the catalyst includes 42-60 wt%, such as 50 wt% of copper oxide, 22-40 wt%, such as 30 wt% of silicon oxide, 10-18 wt%, such as 15 wt% of zinc oxide, 0.5-2 wt%, such as 1 wt% or 1.5 wt% of rare-earth metal oxide, and 1-5 wt
• the invention also provides use of the above catalyst in the liquid phase hydrogenation of acetophenone to produce ⁇ -phenylethanol.
• the catalyst needs to be reduced and activated before having corresponding catalytic activity for the hydrogenation of acetophenone to produce ⁇ -phenylethanol.
• the method for reducing and activating the catalyst according to the present invention comprises: maintaining a volume space velocity of a mixed gas of hydrogen and nitrogen of 300-1000 h -1 , and preferably first increasing the temperature of the reactor to 160-180 °C, keeping the temperature constant for 1-2 h and removing the physical water adsorbed by the catalyst, and followed by introducing a mixed gas of hydrogen and nitrogen with a volume fraction of H 2 not more than 10v%, such as (5v% ⁇ 2v%), to pre-reduce the catalyst for at least 0.5h, such as 1h, 1.5h or 2h, followed by gradually increasing the proportion of hydrogen in the mixed gas of hydrogen and nitrogen, for example, gradually increasing the proportion of hydrogen to 10v%, 20v%, 50v%, 100v% and controlling the hot spot temperature of the catalyst bed in this process to be not exceed 220 °C, and finally raising the temperature to 200-220 °C and reducing in pure hydrogen atmosphere for 2-5h, such as 3h or 4h, to obtain an activated catalyst
• the reaction pressure is 2.5-5MPa (relative pressure), such as 3-5MPa (relative pressure)
• the reaction temperature is 70-140 °C, such as 120-140 °C
• the H 2 /HPA (acetophenone) molar ratio is 2-20:1, such as 5:1, 10:1 or 15:1
• the amount of the catalyst is 0.2-0.6 g HPA ⁇ g cat -1 ⁇ h -1 .
• the catalyst Compared with the prior art, in the process of the liquid phase hydrogenation of acetophenone to produce ⁇ -phenylethanol using the catalyst prepared by the present invention, the catalyst has evenly distributed active components, high dispersity of copper, smooth catalyst pores, weak acidity, excellent activity, excellent selectivity and excellent mechanical strength.
• the addition of a pore-forming agent can effectively improve the mass transfer performance of the catalyst and is beneficial to the improvement of the catalyst activity;
• the use of a composite silicon source can obtain a catalyst for liquid phase hydrogenation with high activity and good mechanical strength;
• the addition of Zn, rare-earth, and alkaline-earth metals in the catalyst is conducive to improving the dispersity of the active component Cu, inhibiting the acidity of the catalyst and improving the activity and selectivity of the catalyst.
• the side pressure strength of the catalyst was measured using a particle strength tester, and the used catalyst was immersed and protected with ethylbenzene to prevent the catalyst from being oxidized.
• the side pressure strengths of 40 pellets of the reacted catalyst were measured and the average value was taken.
• the copper ion content in the hydrogenation solution was measured by inductively coupled plasma-atomic emission spectrometry (ICP).
• the pH of the system was adjusted to > 7.5 using a solution with 10 wt% sodium carbonate, the system was aged at 75 °C for 3h, then filtered, washed, the filter cake was dried at 110 °C for 12h, calcined at 350 °C for 8h, then mixed with 1.5wt% (powder mass) of graphite and pressed into a 3 ⁇ 3 mm cylinder (3mm in diameter and 3mm in height) catalyst, about 200g of Catalyst A was obtained. Based on the oxides, the catalyst contains 55% of copper oxide, 30% of silicon oxide, 10% of zinc oxide, 1% of lanthanum oxide and 4% of magnesium oxide.
• Catalyst reduction the catalyst A was charged in a fixed-bed hydrogenation reactor, and the charging amount of the catalyst was 100 ml.
• the catalyst was reduced under a mixed gas of nitrogen and hydrogen before use. During the reduction, the volume space velocity of the mixed gas was maintained at 300h -1 .
• the temperature of the reactor was first raised to 160 °C and the temperature was maintained for 2h to remove the physical water adsorbed by the catalyst, and then a mixed gas of nitrogen and hydrogen with a H 2 volume fraction of 5v% was added to pre-reduce the catalyst for 1h.
• the hydrogenation raw material was an ethylbenzene solution with 15 wt% acetophenone, and the reaction was carried out under the conditions of a pressure of 2.5Mpa, a temperature of 70 °C, a molar ratio of H 2 /ketone of 5: 1, and a catalyst throughput of 0.3 g HPA /g cat /h.
• the hydrogenation solution was taken every 24h and the copper ion content in the hydrogenation solution was measured.
• the catalyst was removed from the reactor and the catalyst was sieved with a stainless steel sample sieve with a diameter of 2 mm, and the ratio of the mass of the catalyst particles with a particle size of ⁇ 1 mm to the total mass of the catalyst was calculated and used as the catalyst damage rate.
• a particle strength tester was used to determine the side pressure strength of the catalyst after the reaction.
• the results of the hydrogenation reaction and the average copper ion content in the hydrogenation solution are shown in Table 1. See Table 2 for comparison of the catalyst before and after the reaction.
• the pH of the system was adjusted to > 7.5 using a solution with 10 wt% sodium carbonate, the system was aged at 80 °C for 3h, then filtered, washed, the filter cake was dried at 100 °C for 24h, calcined at 400 °C for 12h, then mixed with 1.0wt% (powder mass) of graphite and pressed into a 3 ⁇ 3mm cylinder (3mm in diameter and 3mm in height) catalyst, about 200g of Catalyst B was obtained. Based on the oxides, the catalyst contains 60% of copper oxide, 23% of silicon oxide, 12% of zinc oxide, 0.5% of cerium oxide and 4.5% of calcium oxide.
• the pH of the system was adjusted to > 7.3 using a solution with 10 wt% sodium carbonate, the system was aged at 85 °C for 3h, then filtered, washed, the filter cake was dried at 120 °C for 12h, calcined at 550 °C for 8h, then mixed with 1.2wt% (powder mass) of graphite and pressed into a 3 ⁇ 3mm cylinder (3mm in diameter and 3mm in height) catalyst, about 200g of Catalyst C was obtained. Based on the oxides, the catalyst contains 50% of copper oxide, 35% of silicon oxide, 12% of zinc oxide, 1% of cerium oxide and 2% of barium oxide.
• the pH of the system was adjusted to > 7.2 using a solution with 10 wt% sodium carbonate, the system was aged at 70 °C for 3h, then filtered, washed, the filter cake was dried at 100 °C for 12h, calcined at 450 °C for 6h, then mixed with 1.0wt% (powder mass) of graphite and pressed into a 3 ⁇ 3mm cylinder (3mm in diameter and 3mm in height) catalyst, about 200g of Catalyst D was obtained. Based on the oxides, the catalyst contains 45% of copper oxide, 35% of silicon oxide, 15% of zinc oxide, 2% of lanthanum oxide and 3% of calcium oxide.
• the pH of the system was adjusted to > 7.5 using a solution with 10 wt% sodium carbonate, the system was aged at 90 °C for 3h, then filtered, washed, the filter cake was dried at 110 °C for 12h, calcined at 650 °C for 4h, then mixed with 1.2wt% (powder mass) of graphite and pressed into a 3 ⁇ 3mm cylinder (3mm in diameter and 3mm in height) catalyst, about 200g of Catalyst E was obtained. Based on the oxides, the catalyst contains 40% of copper oxide, 38% of silicon oxide, 18% of zinc oxide, 1.5% of lanthanum oxide and 2.5% of calcium oxide.
• the pH of the system was adjusted to > 7.5 using a solution with 10 wt% sodium carbonate, the system was aged at 70 °C for 3h, then filtered, washed, the filter cake was dried at 110 °C for 24h, calcined at 450 °C for 8h, then mixed with 1.5wt% (powder mass) of graphite and pressed into a 3 ⁇ 3mm cylinder (3mm in diameter and 3mm in height) catalyst, about 200g of Catalyst F was obtained. Based on the oxides, the catalyst contains 52% of copper oxide, 32% of silicon oxide, 10% of zinc oxide, 1% of cerium oxide and 5% of barium oxide.
• the system was aged at 70 °C for 3h, then filtered, washed, the filter cake was dried at 110 °C for 24h, calcined at 450 °C for 8h, then mixed with 1.2wt% (powder mass) of graphite and pressed into a 3 ⁇ 3mm cylinder (3mm in diameter and 3mm in height) catalyst, about 170g of Catalyst G was obtained.
• the results of the hydrogenation reaction of the catalysts of Examples 1-6 and the average copper ion contents in the hydrogenation solution are shown in Table 1, and the comparison of the catalysts before and after the reaction are shown in Table 2.
• the experimental results of the catalysts prepared in Examples 7-12 are basically the same as the corresponding experimental results of Examples 1-6 in sequence, in which the conversion rate of acetophenone were at least 98.1%, and the selectivity to ⁇ -phenylethanol were all at least 99.3%, the detection results of the average copper ion content in the hydrogenation solution were "not detected"; the side pressure strength of the catalysts before the reaction were all at least 188 N/particle, and the side pressure strength of the catalysts after the reaction were all at least 48.5 N/particle.
• catalysts A to F have high activity and can effectively suppress side reactions such as hydrogenolysis to produce ethylbenzene and dehydration to produce styrene, and the catalysts of Comparative Examples 1 to 4 not only have low activity but also poor selectivity.

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